This invention pertains to a novel method-of-use of compounds of Structure I as fungicides for protecting plants from disease.
Processes for the preparation of the compounds described in this invention are disclosed in the following references:
Geffken, D.; Z. Naturforsch, 1983, 38b, 1008 PA0 Geffken, D.; Zinner, G.; Chem. Ber., 1973, 106, 2246 PA0 Geffken, D.; Arch. Pharm,, 1982, 315, 802; PA0 Geffken, D. Z. Naturforsch, 1987, 42b, 1202 PA0 W is O or S; PA0 R.sup.1 is H; C.sub.1 to C.sub.6 alkyl; C.sub.1 to C.sub.6 haloalkyl; C.sub.3 to C.sub.6 cycloalkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 alkynyl; C.sub.2 to C.sub.6 alkoxyalkyl; C.sub.1 to C.sub.3 alkyl substituted with C.sub.3 to C.sub.6 cycloalkyl, phenyl or benzyl, wherein said phenyl or benzyl ring is substituted on the ring with R.sup.6, and the benzylic carbon is substituted with R.sup.7 ; PA0 R.sup.2 is phenyl substituted with R.sup.5 and R.sup.6 ; naphthyl substituted with 1 to 2 groups selected from R.sup.6 ; thienyl substituted with R.sup.5 and R.sup.6 ; furyl substituted with R.sup.6 ; pyridyl substituted with one of the following: PA0 R.sup.1 and R.sup.2 can be taken together, along with the carbon to which they are attached, to form a carbocyclic or heterocyclic ring (containing O, N--R.sup.7, or S) of 5 to 7 ring atoms in which the heterocyclic ring can be fused with an R.sup.5 -substituted benzene ring or an R.sup.6 -substituted thiophene ring, the heteroatom not being attached to the spiro center; and the carbocyclic ring can be fused with 1 or .sup.2 R.sup.5 -substituted benzene rings or with an R.sup.6 -substituted thiophene ring; PA0 R.sup.3 is phenyl substituted with R.sup.10 ; benzyl substituted on the benzylic carbon with a group selected from R.sup.7 and substituted on the phenyl ring with R.sup.10 ; naphthyl substituted with R.sup.10 ; additionally, R.sup.3 can be thienyl substituted with R.sup.10, furyl substituted with R.sup.10, pyridyl substituted with R.sup.10, pyrimidyl substituted with R.sup.10 or pyridazyl substituted with R.sup.10 ; or R.sup.3 can be C.sub.2 to C.sub.10 alkyl or C.sub.5 to C.sub.7 cycloalkyl; PA0 R.sup.4 is hydrogen; formyl; C.sub.2 to C.sub.4 alkylcarbonyl; C.sub.2 to C.sub.4 haloalkylcarbonyl; C.sub.2 to C.sub.4 alkoxyalkylcarbonyl; C.sub.2 to C.sub.4 alkoxycarbonyl; C.sub.2 to C.sub.5 alkylaminocarbonyl; C.sub.1 to C.sub.4 alkylsulfonyl; C.sub.1 to C.sub.4 alkyl; C.sub.4 to C.sub.6 cycloalkyl; phenylaminocarbonyl where said phenyl is substituted with R.sup.10 ; and R.sup.4 can be C.sub.3 to C.sub.4 alkenyl or C.sub.3 to C.sub.4 alkynyl; or PA0 R.sup.3 and R.sup.4 can be taken together, along with the nitrogen atom to which they are attached, to form a pyrrolidino, piperidino or pyrrolo ring substituted with R.sup.10, which rings can be fused to an R.sup.10 -substituted benzene ring; PA0 R.sup.5 is hydrogen; halogen; C.sub.1 to C.sub.12 alkyl; C.sub.1 to C.sub.12 haloalkyl; C.sub.1 to C.sub.12 alkoxy; C.sub.3 to C.sub.12 alkenyl; C.sub.3 to C.sub.12 haloalkenyl; C.sub.3 to C12 alkenyloxy; C.sub.3 to C.sub.12 alkynyl; C.sub.3 to C.sub.12 haloalkynyl; C.sub.3 to C.sub.12 alkylthio; C.sub.1 to C.sub.12 haloalkylthio; C.sub.1 to C.sub.12 haloalkoxy; C.sub.1 to C.sub.12 alkylsulfonyl; C.sub.1 to C.sub.12 haloalkylsulfonyl; nitro; phenyl substituted with R.sup.6 ; phenoxy substituted with R.sup.6 ; phenylthio substituted with R.sup.6 ; cyano; C.sub.3 to C.sub.12 alkynyloxy; C.sub.2 to C.sub.12 alkoxyalkyl; C.sub.2 to C.sub.12 alkoxyalkoxy; phenoxymethyl substituted on the phenyl ring with R.sup.6 ; benzyloxy substituted on the phenyl ring with R.sup.6 ; phenethyloxy substituted on the phenyl ring with R.sup.6 ; phenethyl substituted on the phenyl ring with R.sup.6 ; benzyl substituted on the phenyl ring with R.sup.6 ; C.sub.2 to C.sub.12 carboalkoxy; C.sub.5 to C.sub.6 cycloalkyl; NMe.sub.2 ; or NR.sup.8 R.sup.9 ; PA0 R.sup.6 is hydrogen; 1 to 2 halogen; C.sub.1 to C.sub.4 alkyl; trifluoromethyl; C.sub.1 to C.sub.4 alkoxy; methylthio; nitro; phenoxy; C.sub.2 to C.sub.6 cycloalkyloxy; or C.sub.5 to C.sub.6 cycloalkyl; PA0 R.sup.7 is hydrogen; or C.sub.1 to C.sub.4 alkyl; PA0 R.sup.8 is H; or C.sub.1 to C.sub.4 alkyl; PA0 R.sup.9 is H; phenyl substituted with H; 1-2 halogen; CF.sub.3 ; C.sub.1 to C.sub.2 alkyl; or C.sub.1 to C.sub.2 alkoxy; and PA0 R.sup.10 is 0-2 groups selected from H; CF.sub.3 ; CF.sub.3 O; NO.sub.2 ; CO.sub.2 Me; halogen; C.sub.1 to C.sub.5 alkyl; C.sub.1 to C.sub.5 alkoxy; or CN; provided that when the phenyl ring is disubstituted, one of the alkyl or alkoxy groups is no larger than C.sub.1 ; PA0 2. The method of Preferred 1 wherein PA0 3. The method of Preferred 2 wherein PA0 4. The method of Preferred 3 wherein PA0 R.sup.6 is H or F; and PA0 R.sup.10 is F; H or CH.sub.3. PA0 (1) 5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)-2-thioxo-4-oxazolidinone; and the (S)-enantiomer thereof. ##STR2## (2) 5-methyl-5-phenyl-3-(-N'-phenyl-N'-methylamino)-2-thioxo-4-oxazolidinone; and the (S)-enantiomer thereof. ##STR3## (3) 5-[4-bromophenoxy)phenyl]-5-methyl-3-(phenylamino)-2-thioxo-4-oxazolidinon e; and the (S)-enantiomer thereof. ##STR4## (4) 5-[4-(3-fluorophenoxy)phenyl]-5-methyl-3-(phenylamiono)-2-thioxo-4-oxazoli dinone; and the (S)-enantiomer thereof. ##STR5## (5) 5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione; and the (S)-enantiomer thereof. ##STR6## (6) 5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)-2,4-oxazolidinedione; and the (S)-enantiomer thereof. ##STR7## (7) 5-(2,5-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione; and the (S)-enantiomer thereof. ##STR8## (8) 5-(2-fluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione; and the (S)-enantiomer thereof. ##STR9## (9) 5-[4-(3-fluorophenoxy)phenyl]-5-methyl-3-(phenylamino)-2,4-oxazolidinedion e; and the (S)-enantiomer thereof. ##STR10## 5. This invention also comprises novel compounds of Formula IA, ##STR11## wherein: A is O or NR.sup.4 ; PA0 W is O or S; PA0 R.sup.1 is H; C.sub.1 to C.sub.6 alkyl; C.sub.1 to C.sub.6 haloalkyl; C.sub.3 to C.sub.6 cycloalkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 alkynyl; C.sub.2 to C.sub.6 alkoxyalkyl; C.sub.` to C.sub.3 alkyl substituted with C.sub.3 to C.sub.6 cycloalkyl, phenyl or benzyl, wherein said phenyl or benzyl ring is substituted on the ring with R.sup.6, and the benzylic carbon is substituted with R.sup.7 ; PA0 R.sup.2 is phenyl substituted with R.sup.5 and R.sup.6 ; naphthyl substituted with 1 to 2 groups selected from R.sup.6 ; thienyl substituted with R.sup.5 and R.sup.6 ; furyl substituted with R.sup.6 ; pyridyl substituted with one of the following: PA0 C.sub.1 to C.sub.2 alkyl substituted with phenoxy or phenylthio, said phenoxy or phenylthio being substituted on the ring with R.sup.6 ; PA0 C.sub.1 to C.sub.6 alkyl; or PA0 C.sub.5 to C.sub.7 cycloalkyl; and PA0 R.sup.1 and R.sup.2 can be taken together, along with the carbon to which they are attached, to form a carbocyclic or heterocyclic ring (containing O, N--R.sup.7 or S) of 5 to 7 ring atoms in which the heterocyclic ring can be fused with an R.sup.5 -substituted benzene ring or an R.sup.6 -substituted thiophene ring, the heteroatom not being attached to the spiro center; and the carbocyclic ring can be fused with 1 or 2 R.sup.5 -substituted benzene rings or with an R.sup.6 -substituted thiophene ring; PA0 R.sup.3 is phenyl substituted with R.sup.10 ; benzyl substituted on the benzylic carbon with a group selected from R.sup.7 and substituted on the phenyl ring with R.sup.10 ; naphthyl substituted with R.sup.10 ; additionally, R.sup.3 can be thienyl substituted with R.sup.10, furyl substituted with R.sup.10, pyridyl substituted with R.sup.10, pyrimidyl substituted with R.sup.10, or pyridazyl substituted with R.sup.10 ; or R.sup.3 can be C.sub.2 to C.sub.10 alkyl or C.sub.5 to C.sub.7 cycloalkyl; PA0 R.sup.4 is hydrogen; formyl; C.sub.2 to C.sub.4 alkylcarbonyl; C.sub.2 to C.sub.4 haloalkylcarbonyl; C.sub.2 to C.sub.4 alkoxyalkylcarbonyl; C.sub.2 to C.sub.4 alkoxycarbonyl; C.sub.2 to C.sub.5 alkylaminocarbonyl; C.sub.1 to C.sub.4 alkylsulfonyl; C.sub.1 to C.sub.4 alkyl; C.sub.4 to C.sub.6 cycloalkyl; phenylaminocarbonyl where said phenyl is substituted with R.sup.10 ; and R.sup.4 can be C.sub.3 to C.sub.4 alkenyl or C.sub.3 to C.sub.4 alkynyl; or PA0 R.sup.3 and R.sup.4 can be taken together, along with the nitrogen atom to which they are attached, to form a pyrrolidino, piperidino or pyrrolo ring substituted with R.sup.10, which rings can be fused to an R.sup.10 -substituted benzene ring; PA0 R.sup.5 is hydrogen; halogen; C.sub.1 to C.sub.12 alkyl; C.sub.1 to C.sub.12 haloalkyl; C.sub.1 to C.sub.12 alkoxy; C.sub.3 to C.sub.12 alkenyl; C.sub.3 to C.sub.12 haloalkenyl; C.sub.3 to C.sub.12 alkenyloxy; C.sub.3 to C.sub.12 alkynyl; C.sub.3 to C.sub.12 haloalkynyl; C.sub.3 to C.sub.12 alkylthio; C.sub.1 to C.sub.12 haloalkylthio; C.sub.1 to C.sub.12 haloalkoxy; C.sub.1 to C.sub.12 alkylsulfonyl; C.sub.1 to C.sub.12 haloalkylsulfonyl; nitro; phenyl substituted with R.sup.6 ; phenoxy substituted with R.sup.6 ; phenylthio substituted with R.sup.6 ; cyano; C.sub.3 to C.sub.12 alkynyloxy; C.sub.2 to C.sub.12 alkoxyalkyl; C.sub.2 to C.sub.12 alkoxyalkoxy; phenoxymethyl substituted on the phenyl ring with R.sup.6 ; benzyloxy substituted on the phenyl ring with R.sup.6 ; phenethyloxy substituted on the phenyl ring with R.sup.6 ; phenethyl substituted on the phenyl ring with R.sup.6 ; benzyl substituted on the phenyl ring with R.sup.6 ; C.sub.2 to C.sub.12 carboalkoxy; C.sub.5 to C.sub.6 cycloalkyl; NMe.sub.2 ; or NR.sup.8 R.sup.9 ; PA0 R.sup.6 is hydrogen; 1 to 2 halogen; C.sub.1 to C.sub.4 alkyl; trifluoromethyl; C.sub.1 to C.sub.4 alkoxy; methylthio; nitro; phenoxy; C.sub.2 to C.sub.6 cycloalkyloxy; or C.sub.5 to C.sub.6 cycloalkyl; PA0 R.sup.7 is hydrogen; or C.sub.1 to C.sub.4 alkyl; PA0 R.sup.8 is H; or C.sub.1 to C.sub.4 alkyl; PA0 R.sup.9 is H; phenyl substituted with H; 1-2 halogen; CF.sub.3 ; C.sub.1 to C.sub.2 alkyl; or C.sub.1 to C.sub.2 alkoxy; and PA0 R.sup.10 is 0-2 groups selected from H; CF.sub.3 ; CF.sub.3 O; NO.sub.2 ; CO.sub.2 Me; halogen; C.sub.1 to C.sub.5 alkyl; C.sub.1 to C.sub.5 alkoxy; or CN; provided that when the phenyl ring is disubstituted, one of the alkyl or alkoxy groups is no larger than C.sub.1 ; provided that PA0 6. A compound of Formula IA wherein PA0 provided that when R.sup.2 is unsubstituted phenyl, R.sup.1 is not methyl. PA0 7. A compound of Formula IA wherein PA0 provided that when R.sup.2 is unsubstituted phenyl, R.sup.1 is not methyl. PA0 8. A compound of Formula IA wherein PA0 (1) 5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)-2-thioxo-4-oxazolidinone; and the (S)-enantiomer thereof. ##STR12## (2) 5-methyl-5-phenyl-3-N'-phenyl-N'-methylamino)-2-thioxo-4-oxazolidinone; an d the (S)-enantiomer thereof. ##STR13## (3) 5-(4-(4-bromophenoxy)phenyl)-5-methyl-3-(phenylamino)-2-thioxo-4-oxazolidi none; and the (S)-enantiomer thereof. ##STR14## (4) 5-[4-(3-fluorophenoxy)phenyl]-5-methyl-3-(phenylamino)-2-thioxo-4-oxazolid inone; and the (S)-enantiomer thereof. ##STR15## (5) 5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione; and the (S)-enantiomer thereof. ##STR16## (6) 5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)-2,4-oxazolidinedione; and the (S)-enantiomer thereof. ##STR17##
No particular utility for the compounds is described in the above references.
A new process for the preparation of these compounds is also disclosed in this application.
Compounds related to I are broadly disclosed as medicines, agrochemicals and microbicides in Japanese Patent 61/200978-A, and as general biocides in EP 249328-A. However, these applications do not encompass compounds of the instant invention, nor do they suggest the use of the compounds of this invention as fungicides particularly effective for
the protection of crops against disease.